A Windmill-Shaped Hexacopper(II) Molecule Built Up by Template Core-Controlled Expansion of Diaquatetrakis(μ₂-adeninato-<i>N</i>3,<i>N</i>9)dicopper(II) with Aqua(oxydiacetato)copper(II)

The windmill-shaped hexanuclear copper(II) cluster {(H2O)2Cu2(μ3-(Ade)4[Cu(oda)(H2O)]4}·6H2O (1-o) has been synthesized in aqueous medium by in situ core-controlled expansion of the neutral building block Cu2(μ2-N3,N9-Ade)4(H2O)2 (2) with Cu(oda)(H2O) (3-o) (Ade = adeninato(1−) and oda = oxydiacetato(2−) ligands). Crystal data for 2-b (2·5H2O): triclinic, space group P1̄; a = 9.374(1), b = 9.440(1), c = 10.326(1) Å; α = 78.72(1), β = 76.77(1), γ = 63.51(1)°; final R1 = 0.059; T = 100(2) K. Crystal data for 1-o: monoclinic, space group P21/n; a = 15.203(2), b = 10.245(1), c = 19.094(2) Å; β = 101.61(1)°; final R1 = 0.049; T = 293(2) K. The X-shaped hexanuclear molecule consists of a central core (2) and four terminal arms (3-o) linked together by bridging μ3-N3,N7,N9-Ade ligands. There are three crystallographic independent metal atoms (two terminals, one central). All Cu(II) atoms exhibit a 4 + 1 coordination, of which one is an aqua apical ligand. The basal coordination sets complete the CuN4 + O or CuO3N + O chromophores for the central or terminal metal atoms, respectively. Thermal stability and spectral and magnetic properties were also studied. Analogous compounds to 1-o with tridentate or tripodal tetradentate ligands L2-, instead of oda, have also been synthesized.风车形六核铜(II)簇合物{(H₂O)₂Cu₂(μ₃-(Ade)₄[Cu(oda)(H₂O)]₄}·6H₂O (1-o) 于水相介质中，通过中性构筑基元Cu₂(μ₂-N3,N9-Ade)₄(H₂O)₂ (2) 与Cu(oda)(H₂O) (3-o) 发生原位核心可控拓展反应合成得到，其中Ade为腺嘌呤阴离子(1−)（adeninato(1−)）配体，oda为氧二乙酸根(2−)（oxydiacetato(2−)）配体。 针对2-b（2·5H₂O）的晶体学参数如下：三斜晶系，空间群P-1；晶胞参数a=9.374(1)、b=9.440(1)、c=10.326(1) Å；晶胞角α=78.72(1)°、β=76.77(1)°、γ=63.51(1)°；最终R1因子为0.059；测试温度T=100(2) K。 针对1-o的晶体学参数如下：单斜晶系，空间群P2₁/n；晶胞参数a=15.203(2)、b=10.245(1)、c=19.094(2) Å；β=101.61(1)°；最终R1因子为0.049；测试温度T=293(2) K。 该X形六核分子由一个中心核(2)与四个端基臂(3-o)通过桥联μ3-N3,N7,N9-Ade配体连接构成。体系中存在三个晶体学独立的金属原子（两个端基金属原子与一个中心金属原子）。所有Cu(II)原子均表现出4+1配位模式，其中一个配位位点为轴向水分子配体。对于中心金属原子与端基金属原子，其赤道配位环境分别构成CuN4+O与CuO3N+O配位构型。本研究同时对该簇合物的热稳定性、光谱学与磁学性质进行了表征。以三齿或三脚架型四齿配体L²⁻替代oda配体得到的1-o类同构化合物也已成功合成。